Process for breaking petroleum emulsions employing certain polyepoxide treated amine-modified thermoplastic phenol-aldehyde resins



PROCESS FOR BREAKING PETROLEUM EMUL- SIONS EMPIDYING CERTAIN- POLYEPOXIDE TREATED AMlNE-MODIFIED THERMOPLASTIC PHENOL-ALDEHYDE RESINS Melvin De Groote, University City, and Kwan-Ting Shen, Brentwood, Mo'., asslgnors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application February 24, 1953 Serial-No. 338,575

20 Claims. c1. esp-s38) The present'invention is a eontinuation-in-part of our co-pending applieation Serial No. 305,079. filed August 18, 1952, now abandoned.

The present invention is concerned with demulsification which involves the use of certain polyepoxide-treated amine-modified thermoplastic phenol-aldehyde resins for the resolution of petroleum emulsions. More specifically, this aspect of the invention involves the breaking of emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including products obtained by the method of first condensing certain phenol-aldehyde resins, hereinafter described in detail, with certain basic non-hydroxylated polyamines, having at least one secondary amino group and having not more than 32 carbon atoms in any group attached to any amino nitrogen atom, hereinafter described in detail, and formaldehyde, which condensation is followed by reaction of the; resin condensate with certain phenolic polyepoxides, alsohereinafter described in detail, and cogenerically associated compounds formed in the preparation of the polyepoxides.

In preparingdiepoxidesor the low molal polymers one does usually obtain cogeneric materials which may include monoepoxides. However, the c'ogeneric mixture is invariably characterized by the fact thatthere hen the average, based on the molecular weight, of course, more than one epoxide group per molecule.-

A more limited aspect of the invention is represented by the breaking of emulsions by the use of the reaction product of (A) an amine-modified phenol-aldehyde resin condensateas described,-and (B) a'member of the class consisting'of (1) compoundsof the following formula:

and (2) cogenerically associated compounds formedin the preparation of (1) preceding. I

It so happens that the bulk of informafon concerned with the preparation of compounds havingtwo oxirahe rings appears in-the patent'literature' and for: the most part in the recent patent literature. Thus, in the subsequent text, there are numerous references to such patents for purpose'o f'snpplying information and also for'purpose of brevity. I I

Notwithstanding'ftheifact that subsequent data will be presented in' considerable detail, yet ,the description becomes somewhat involved and certain'facts shouldbe keptin mind. The epoxides, and particularly. the 'di@ epoxides may have. no bridge between the phenolic nuclei as in the-case'of a diphenyl derivative or may have a variety of connecting bridges, i.e., divalent "ice linking radicals. Our preference is that either diphenyl compounds be employed or else compounds where the divalent link is obtained by the removal of a carbonyl oxygen atom as derived from a ketone or aldehyde.

If it were not for the expense involved in preparing and purifying the monomer we would prefer it to any other form, i. e., in preference to the polymer or mixture of polymer and monomer.

Stated another way we would prefer to use materials of the kind described, for example in U. S. Patent 2,530,- 353, dated November 14, 1950. Said paten: describes compounds having the general formula 3 wherein R is an aliphatic hydrocarbonbridge, each n independently has one of the values 0 and 1, and X is an 7 alkyl radical containing from 1 to 4 carbon atoms.

The list of patents hereinafter referred to in the text as far as polyepoxide goes, is as follows:

U. 8. Patent No. Dated Inventor July 6, l939-.-.-...-- Scholar. December 13 1938..... Mtkeska et sl September 25, 1939--.- Do.

April 2, 1940..... D0.

Cohen et al .Rosen et al .R n.

.Brltton et al W g at De Groote at al. Swern et al. Wai r-v Do. Dtetzler. Mtkeska at al. Dlotzler at al. Bock et al. Bender et al. Stevens et al.

Do. Do. Dtetzler. Ha ens. August 14, 1951.. Do Groote at al November 20, 19 Newey at 81. January 8, 1952. Albert. January 8, l952..-.--- Zooh. January 22,- 1952.. .Greenlee.

The compounds having two oxirane rings and employed for combination with the reactive amine-modified phenol-aldehyde resin condensates as herein described are compounds of the following formula and cogenerically the divalent associated compounds formed in their preparation:

radical, the'divalent' sulfone radical, and the divalent monosulfide radical --S-,- the divalent radical Patented Nov. 20, 1956 and the divalent disulfide radical S-S-; and R is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol bon atoms; n representsaninteger selected from the class of zero and, 1, and n' represents awhole number not greater than 3. The above mentioned compounds and those cogenerically associated compounds formed in their preparation are thermoplastic and organic solventsoluble. Reference to.being thermoplastic characterizes them as being liquids at ordinary temperature ;or readily convertible to liquids by merelyvheating below the point of pyrolysis and thus differentiates them from infusibie .resins.

Reference to being soluble in an organic solvent means any of the usual organic solvents, such as alcohols, v

condensate) ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusibieu .Eurthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings before reacting with the aminemodified resin. In such instances, of course, the solvent selected (would have to be one which is not susceptible to oxyalkylation, as for example, kerosene, benzene, toluene; .dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglyeol diethylether,- and dimethoxytetraethyleneglycol. j-- I The expression epoxy is not usually limited to the 1,2- epoxyring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word 'epoxy unless indicated otherwise, will be used tomean the oxiranering, i.e., the 1,2-epoxy ring. Furthermore, when a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2-

epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint It well may be that even though the previously suggested formula .represents the principal component, "or

- times it is desirable to add a small amount of acetone to components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar' compounds, generally of much higher molecularweight, have been described as complex resinous epoxides which are polyether derivatives of polyhyric phenols containing an averagepf more than one cpoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. See U. S. Patent No. 2,494,295, dated January 10, 1950, to Greenlee. the monomers or the low molal members of such series and generaliy'contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent in the usual The compounds here included are limited to Patent No. 2,494,295 describes products wherein the epoxide derivative can combine with a sulfonamide resin. The invention in said U. S. Patent 2,494,295, of course, is to obtain ultimately a suitable resinous product having the characteristics of a comparatively insoluble resin.

Having obtained a reactant having generally 2 epoxy rings as depicted in the last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any amine-modified phenolaldehyde resin by virtue of the fact that there are always present reactive hydroxyl groups which are part of the phenolic nuclei'and there maybe present reactive hydrogen atoms attached to, a nitrogen atom, or an oxygen. atom,

depending on the presence of a hydroxyiated group or secondary amino group. I I

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i.e., the compound having two oxiranerings and an amine condensate.- Proceeding with the example previously described it is obvious the reaction ratio of two moles of the amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

(condensate include water, or'for that.mat ter,'al solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyace'tic'acid, etc. In"other words, the nitrogen groups present, whether two ormore, may or maynot be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form such as the acetate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those-resultingfrom gelation or cross iinking. Not only does this property serve to differentiate from instances where an'insoluble material is desired, ,but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly dispersible in 5% gluconic acid. For in stance, the products freed from any solvent can be shaken with 5 to 20 times their weight of 5%distilled water at ordinary temperature and show at least some tendency towards being self-dispersing. Thesolvent which is'gener'ally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance,

1 parts or xylene and 20 parts of methanol, or 70 parts of xylene and 30 parts of methanol, can be used. Somethe xylene-methanol mixture, for instance, 5% to 10% of acetone. H v

The polyepoxide-treated condensates obtained in the manner described are, in turn, exyalkylation-susceptible and valuable derivatives can be obtained by further reaction with ethylene oxide, propylene oxide, ethylene imine,etc. l, a I t Similarly, .the polyepoxide-deriv'ed compounds can. be reacted with a'product having both a nitrogen group and a 1,2-epoxy group, such asB-dialkylaminoepoxypropane. See U.- S. PatentNo. 2,520,093, dated August 22, 1950, i0 Gro1l..;,' ,,3

, Although :the herein described, products have innumber of industrial, applications, they are .of particularvalue for resolving petroleum emulsions. of the waterit thermosetting resins. Note, for example, that said U. 8. 7 011 type that are commonly to as cut oil,i-roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid wash-- ing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for example for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., combination with water or particularly in the form of a lowmolal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sufiiciently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate. may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylethcr, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking andsurface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience what is said hereinafter will be divided into eight parts with Part 3, in turn, being divided into three subdivisions:

Part 1 is concerned with our preference in regard to the polyepoxide and particularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

Part 3, Subdivision A, is concerned with the preparation of monomeric diepoxides, including 'Table I;

Part 3, Subdivision B, is concerned with the preparation of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II; I

Part 3, Subdivision C, is concerned with miscellaneous phenolic-reactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin.

Part 5 is concerned with basic nonhydroxylated polyamines having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and

Part 6 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then'subjected to reaction with polyepoxides;

two preceding types of materials and examples obtained by such reaction. Generally speaking, this involves nothing more than a reaction between 2 moles of a previously prepared amine-modified phenol-aldehyde resin condensate as described, and one mole of a polyepoxide so as to yield a new. and larger resin molecule, or comparable As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solventsoluble liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from'any monoepoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes -what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. It is generally obtained from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of the epoxides usually results in the formation of a co generic mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually expensive. If monomers were available commercially at a low cost, or if they could be prepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been prepared and described in the literature and will be referred to subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fullyrecognize that there may be present, and probably invariably are present, other low molal polymers in comparatively small amounts. Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present. Indeed, the mixture can be prepared freefrom monomers and still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances where the phenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate asecond class, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. All the various known classes may be used but our preference rests with these classes due to their availability and ease of preparation, and also due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our preference is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol A. It can be used as such, or the monomer can be separated by an added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. The formula for this compound is CH; II H H l H H I! no o-g-o o oc owofl an: 0

Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with the 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2 isomers being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, L) wit, Part 1, and in succeeding parts, the text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived from th other groups illustrated for the reason that nothing more than mere substitution of one compound for the other would be required. Thus, what is said hereinafter, although directed to one class or a few classes, applies with equal force and effect to the other classes of epoxide reactants.

If sulfur-containing compounds are prepared they should be freed from impurities with considerable care for the reason that any time that a low-molal sulfur-containing compound can react with epichlorohydrin there may be formed a by-product in which the chlorine happened to be particularly reactive and may represent a product, or a mixture of products, which would be unusually toxic, even though in comparatively small concentration.

PART 2 Treatment with epichlorohydrin, for example, does not yield this product initially but there is an intermediate produced which can be indicated by the following structure:

Treatment with alkali, of course, forms the epoxy ring. A number of problems are involved in attempting to produce this compound free from cogeneric materials of related composition. The difliculty stems from a number of sources and a few of the more important ones are as follows:

(1) The closing of the epoxy ring involves the use of caustic sode or the like which, in turn, is an effective catalyst in causing the ring to open in an oxyalkylation reaction.

Actually, what may happen for any one of a number of reasons is that one obtains a product in which there is only one epoxide ring and there may, as a matter of fact,

be more than one hydroxyl radical as illustrated following compounds:

(2) Even if one starts with the reactants in the preferred ratio, to wit, two parts of epichlorohydrin to one part of bis-phenol A, they do not necessarily so react and as a result one may obtain products in which more than two epichlorohydrin residues become attached to a single bis-phenol A nucleus by virtue of the reactive hydroxyls present which enter into oxyalkylationreactions rathe than ring closure reactions.

(3) As is well known, ethylene oxide in the presence of alkali, and for that matter in the complete absence of water, forms cyclic polymers. Indeed, ethylene oxide can produce a solid polymer. This same reaction can, and at times apparently does, take place in connection with compounds having one, or in the present instance,

two substituted oxirane rings, i. e., substituted 1,2 epoxy rings. Thus, in many ways it is easier to produce a polymer, particularly a mixture of the monomer, dimer and trimer, than it is to produce the monomer alone.

(4) As has been pointed out previously, monoepoxides may be present and, indeed, are almost invariably and inevitably present when one attempts to produce polyepoxides, and particularly diepoxides. The reason is the one which has been indicated previously, together with the fact that in the ordinary course of reactiona diepoxide, such as may react with a mole of bis-phenol A to give a monoepoxy structure. Indeed, in the subsequent text immediately following reference is mada to thedimers, trimers and tetramers in which two epoxide groups are present. Needless to say, compounds can be formed which correspond in every respect except that one terminal epoxide group is absent and in its place is a grouphaving one chlorine atom and one hydroxyl group, or else two hy- V droxyl groups, or an unreacted phenolic ring.

(5) Some reference has been made to the presence of a chlorine. atom and although all effort is directed towards the elimination of any chlorine-containing molecule yet it is apparent that thisv is often an ideal approach rather than a practical possibility. Indeed, the same sort of reactants are sometimes employed to obtain products in which intentionally there is both an epoxide group and a chlorine atom present. See U. S. Patent No. 2,581,464, dated January 8, 1952, to Zech.

What has been said in regard to the theoretical aspect is, of course, closely related to the actual method of preparation which is discussed in greater detail in Part 3, particularly subdivisions A and B. There can beno clear line between the theoretical aspect and actual preparative steps. what has been said in Part 1, immediately preceding reference will be made to a typical example which already has been employed for purpose of illustration. The particular example is by the However, in order to summarize or illustrate 10 It is obvious that two moles of such material combine Such a compound is comparable to other compounds havreadily with one mole of bis-phenol A, ing both the hydroxyl and epoxy ring such as 9,10-epoxy cm octadecanol. The ease with which this type of compound H 6 OH polymerizes is pointed out by U. S. Patent No. 2,457,329,

I dated December 28, 1948, to Swern et al.

OH; The same difliculty which involves the tendency to polyto produce the product which is one ste further along, at merize on e P of compounds having a reactive s least, towards polymerization. In other words, one prior and a y y radical y be illustrated y compounds example shows the reaction product obtained from one where, instead of the Minute g (L p y g) there mole of the bisphenol A and two moles of epichlorohydrin. 10 is Present a L P Y fing- Such compounds are deriva- This product in turn would represent three moles of bisiii/e8 0f irimeihyleiie Oxide rather than ethylene Oxidephen lAand four moles of epichlorohydrin. See U. S. Patents Nos. 2,462,047 and 2,462,048, both For purpose of brevity, without going any further, the dated February 15, 1949, to id next formula is in essence one which, erha sin an ideal- At the expense of repetition of what pp P ized way, establishes the composition of resinous products i y. it y be well to recall that these materials y available under the name of Epon Resins as now sold in y from simple soluble non-resinous to complex the open market. See, also, chemical p m hl titl d soluble resinous epoxides which are polyether derivatives Epon Surface-Coating Resins, Shell Chemical Corporaof polyhydric phenols containing an average of more than tion, New York city. The word Epon is a registered one epoxide group per molecule and free from functional trademark of the Shell Chemical Corporation. groups other than epoxide and hydroxyl groups. The

For the purpose of the instant invention, u may repreformer are here included, but the latter, i. e., highly sent a number including zero, and at the most a. low resinous or insoluble types, are not. number such as 1, 2 or 3. This limitation does not exist In summary then in light of what has been said, comin actual efforts to obtain resins as differentiated from the pounds suitable for reaction with amines may be sumherein described soluble materials. It is quite probable marized by the following formula:

that in the resinous products as marketed for coating use or for greater simplicity the formula could be restated the value ofn is usually substantially higher. Note again thus:

H, H H s H. g Hi what has been said previously that any formula is, at in which the various characters have their prior signifibest, an over-simplification, or at the most represents canoe and in which R10 is the divalent radical obtained perhaps only the more important or principal constituent by the elimination of a hydroxyl hydrogen atom and a or constituents. These materials may vary from simple nuclear hydrogen atom from the phenol non-resinous to complex resinous epoxides which are polyether derivatives of polyhydric phenols containing an 7 on average of more than one epoxide group per molecule and free from functional groups other than epoxide and hy- I. droxyl groups.

Referring now to what has been said previously, to wit, in which and represent a member of the class compounds having both an epoxy ring or the gquivalent consisting Of hydrogen and hydrocarbon substituents Of and also a hydroxyl group, one need go no furthe tha the aromatic nucleus, said substituent member having to id h reaction product of not over 18 carbon atoms; n represents an integer selected from the class of zero and 1, and n represents a whole g O B g g g number not greater than T g b 3 and bisphenol A in a mole-for-mole ratio, since the initial Subdivision A reactant would yield a product having an unreacted epoxy The preparations of the diepoxy derivatives of the diring and two reactive hydroxyl radicals. Referring again phenols, which are sometimes referred to as diglycidyl to a previous formula, consider an example where two ethers, have been described in a number of patents. For moles of bisphenol A have been reacted with 3 moles of convenience, reference will be made to two only, to wit, epichlorohydrin. The simplest compound formed would aforementioned U. S. Patent 2,506,486, and aforemenbe thus: tioned U. S. Patent No. 2,530,353.

p a p Purely by way of illustration, the following diepoxides, particularly the aforementioned U. S. Patents Nos.

or diglycidyl ethers as they are sometimes termed, are included for purpose of illustration. These particular 2'575'558 and Compounds are dmribcd in the mo Pam, inst met In light of aforementioned U. S. PatentNo. 2,575,558, lioned. 5 the following examples can be specified by reference to TABLEI Er- Potent nmple Diphenol Dlglycidyl other refernumber 7 once 0 H 486 hrhggd i fim on 0.8.0 Mouse m) on) zdumd ii'i 2.1mm 0- 0 2m: o'ii n n c r o I 486 ignic i niig ofishniomi. e.-. onlic 3mc.aide3:::::::::: 2630:8113

Subdivision 8 As to the preparation of low-molal polymeric epoxides or mixtures reference is made to numerous patents and 25 the formula therein provided one still bears in mind it is in essence an over-simplification.

TABLE [1 H 0 -O-O 0B|-[R].-R|0O(5O 0B|[R].R1O-OC--O H: H H; H! a Ha H H:

(in which the characters have their previous significance) Example -Ri0- lrom HRlOH -R- n n Remarks number B1 Hydroxy bentene CH; 1 0,1,2 Phenol known as bis-phenol A. Low V polymeric mixture about 96 or more where 1l'=O, remainder largely where b n'=1, some where n=2.

B2. ..do CH; 1 0, 1, 2 Phenol known asbis-phenol 13. See note regarding 131 above.

B8 Orthobutylphenol CH; 1 0,1,2 Even though 11' is preferably 0, yet the usual reaction product might well contaln materials where 'n is l, or to a lesser degree 2. in.

B4 Orthoamylphenol EH; 1 0,1,2 Do.

B5 Orthooctylphenol EH; 1 0,1,2 Do.

B6 Orthononylphenol EH; 1 0,1,2 Do.

B7 Orthcdodecylphenol EH1 1 0,1,2 Do.

B8 Metacresol OH; 1 0,1,2 Bee prior note. This phenol used as |J initial material is known as bis-phenol C. For other suitable bis-phenols see U. 3. Patent 2,564,191.

B9 -.do CH; 1 0,1,2 See prior note.

B10 Dibutyl (ortho-pere) phenol. H 1 0,1,2 Do.

TABLE II (continued) Example R O- from ERrOH -R n n' Remarks number B11 Diamyl (ortho-pare) phenol. 1 0,1,2 Do.

1312.--.-. Dioctyl (ortho-pera) phenol. I! 1 0,1,2 Do.

B13 Dinonyl (ortho-para) phenol. 15 1 0,1,2 Do.

3814..-.-- Diamyl (ortho-pma) phenolg 1 0,1,2 Do.

315 do H 1 0,1,2 Do.

1816...... Hydroxybenzene E 1 0,1,2 Do.

1111....-- Dlamyl phenol (ortho-pora). 'sB- 1 0,1,2 Do.

1318.. -.do S- 1 0, 1, 2 Do. 1319---... DlbutylphenoKortho-pera). g 15 1 0,1,2 Do.

1120 an H H 1 0,1,2 Do.

1321 DlnonylphenoKortho-para). 1g 1g 1 0,1,2 Do;

B22 Hydroxy benzene E 1 0,1,2 Do.

1323...... do None 0 0, l, 2 D0.

1324...... Ortho-lsopropyl phenol CH; 1 0,1,2 Beeprlor note. As to greparatlon 014,4- isopropylldene btslsopropylphenol) see U. 8. Patent 0. 2,4s2,1 -3, dated J; Sept. 27, 1949, to Dletzler.

B25 Pam-octyl phenol 'CHIB'-CHI 1 0,1,2 Seeprior note. (Asto pregaaratlon otths phenol sulfide see Patent No. 2,488,134, dated NOV. 15, 1949, to Mlkeska et a1.)

B26 Hydroxybeuzeno CH: 1 0,1,2 See prior note. (As to re aration ol the ghenol sulfide see Patent No. ,526,645.)

Subdivision C may be illustrated by a phenol of the following composi The prior examples have been limited largely to those in which there is no divalent linking radical, as in the case of diphenyl compounds, or where the linking radical is derived from a ketone or aldehyde, particularly 11 kctone. Needless to say, the same procedure is employed in converting diphenyl into a diglycidyl ether regardless of the nature of the bond between the two phenolic nuclei. For purpose of illustration attention is directed to numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepoxide, reactant.

As previously pointed out the initial phenol may be substituted, and the substituent group in turn may be a cyclic group such as the phenyl group or cyclohexyl group as in the. instance of cyclohexylphenol or phenylphenol. Such substituents are usually in the ortho position and tion:

CH3 J, (BB:

HO OH Similar phenols which are monofunctional, for instance, paraphenyl phenol or paracyclohexyl phenol with an additional substituent in the ortho position, may be employed i subsequent reaction with epichlorohydrin, etc.

Other samples include:

wherein R1 is a substituent selected fromthe class consisting of secondary butyl and tertiary butyl groups and R: is a substituent selected from the class consisting of alkyl. cycloalkyl, aryl, aralkyl, and alltaryl groups, and wherein said alkyl group contains at least 3 carbon atoms.

See U. S. Patent No. 2,515,907.

13(00111000 (0r t )|Tl in which the CsHn groups are secondary amyl groups. See U. S. Patent No. 2,504,064.

wherein R is a member of the group consisting of alkyl, and alkoxy-alkyl radicals containing from 1 to 5 carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U. S. Patent No. 2,526,545.

OH OH R: R1 6 R1 in wherein R1 is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R2 is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alltaryl groups. See U. S. Patent No. 2,515,906.

CH=OH See U. S. Patent No. 2,515,908.

HOH

16 As to sulfides, the following compound is of interest:

Ol ll 05 11 See U. S. Patent No. 2,331,448.

As to descriptions of various suitable phenol sulfides, reference is made to the following patents: U. S. Patents Nos. 2,246,321, 2,207,719, 2,174,248, 2,244,021, and 2,195,539.

As to sulfones, see U. S. Patent No. 2,122,958.

As to suitable compounds obtained by the use of formaldehyde or some other aldehyde, particularly compounds such as Al yl Alkyl in which R5 is a methylene radical, or a substituted methylene radical which represents the residue of an aldehyde and is preferably the unsubstituted methylene radical derived from formaldehyde. See U. S. Patent No. 2,430,002.

See also U. S. Patent No. 2,581,919 which describes di(dialkyl cresol) sulfides which include the monosulfides, the disulfides, and the polysulfides. The following formula represents the various dicresol sulfides of this invention:

OH OH: OH: OH

in which R1 and R2 are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R1 and Rs each preferably contain 3 to about 10 carbon atoms, and x is 1 to 4. The term sulfides as used in this text, therefore, includes monosulfide, disulfide, and polysulfides.

PART 4 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; Rrepresents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 15 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent. bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or

spams? :tylene', but requires an oxygenated solvent such as" a low molat alcohol, dioxane, or diethyleneglycol diethylether: Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. Scc.EXample 9a of U. S. Patent No. 2,499,365, dated M a 7, 1950, to De Groote and Keiser.

The resins herein empl oyed as raw materials must be soluble in a nonokyg'e'natetf solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make. a so lubility test on commercially available resins, or else pie-para resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote' and Keiser. In said patent there are described oxyalltylatiomsusceptible, fusible, nonoxygefiatedorganie solvent-soluble, waterinsoluble, low-stage phenolaldehy de resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. These resins are difunctional only in regard to methylol-forming reactivity, are derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula The basic nonhydroaylated amine may be designed thus:

In conducting reactions of this kind one does ,not necessarily .obtain a hundredpercent yield for obvious reasons; Certain-aideaeacn'on's may take place. For instance, 2 molesof combine with-one mole of the aldehyde, or only one mole of the amine may 'cbmb'ine the res'inaholecule, or'even to sway slight ex- .18 tent, if at all,- 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

E si- 011g OLE GE- OH @l w ll 19 As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

on on on QRIHEQRIH in which R' is the divalent radical obtained from the particular aldehydeemployed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst ,or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly,.if a strong base is .used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidlyin the presence of a small amount of a free base. The amount may be as. small as a 200thof a percent and as much as a few .10ths of a percent. Sometimes moderate increasein caustic soda and caustic potash may be used. However,- the most desirable procedure in'praeticallyevery case is to have the resin neutral. In preparing resins one does not get a single polymer, i. .e., onehayin'g just 3 :units, or just 4 units, or just 5 units, or just -6 Eunits, .etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimerand pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for=example, 3.6, 4.5 or 5.2.

In theactual manufacture of the resins we found no reasonzfornusing' other than those which are lowest in :price :and most readily available commercially. For

purposes of convenience suitable resins are characterized in the following table:

TABLE III Moi. wt. EX. Rm i RS111 ample R Position derived 7: molecule number oi R iromascd on n+2) Pbenyl Para.-.. Formal- 8. 992. 5

dehyde. Tertiary butyl do 8.5 882. 5 Secondary butyl... Ortho..- ...do..-.... 3. 5 882. 5 Cyclo-hexyl P 3. 5 1, 025. 5 Tertiary amyl 3. 5 959. 5 Mixed secondary 0 3. 5 805. 5

and tertiary amyl. i lrilyr i a: er ary Octyl 8. 5 1, 190. 5 Nonyl..... 8. 5 1, 267. 5 ecyl d 8. 5 1, 344. 5 od do..... do 8.5 1,498.5 -.-do...-. Ac s ata lde- 8. 5 945. 5

y e. 140 Tertiary amyl. do..... ...do 8.5 1,022.5 Wily 1 3 3"" ii it??? 160 art 11 o u ty aldehyde 17a Tertiary amyl ...do.-... ...do....... 8.5 1,148.5 18a Non l .-.do. ...do 8. 5 1, 455. 5 19a Tertiary butyl ...do..... Pro lon- 8. 5 1,008. 5

. aide yde 4. 2 I, 083. 4 e 2 1, 430. a 4 a 1, 094. 4 4. s 1, 189. e 4. s 1, 570. 4 1. 5 004. 0 1. 5 646. 0 I. 5 653. 0 1. 5 688.0

2. 0 1, 028. 0 2. 0 860. 0 2. 0 635. 0 ehyde 38a Amyl do n v 2.0 592.0 390 Her L. 2.0 748.0 40a Cyan-beryl ...do..... 6 n 2. 0 740.0

PART 5 Ashas been pointed out, the amine herein employed as a reactant is a basic secondary polyamine and prefer-' ably a strongly basic secondary polyamine free from hydroxyl groups, free from primary amino groups, free from 55 substituted imidazoline groups, and free from substituted tetahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalent are alkyl alicyclic, arylalkyl, or heterocyclic in character.

Previous reference has been made to a number of polyamines which are satisfactory for use as reactants in the instant condensation procedure. The cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be-as many as 5. 6 or 7 nitrogen atoms. Such amines are susceptible to terminal alkylation of the equivalent,

20 from dichloroethyl ethers in which the divalent radical has a carbon atom charm-interrupted by an oxygen atom:

CH: /OHs Ncsnsgc gHeN tommcimgcmmwmr car. can

gnoasngoin cm on. NC1H4OCsH4N CsHs Cs s normo oimn OH; OH: H propyleneNpropylene CHs\ OHs N CsHsNCsHsNOsHah/ H H CHs\ CH1 N CsHsNCsHsN CsHsNCsIhN H E H by theme of an alkylating agent or the comparable procedure'inwhich a halide is used.

" What has been said previously may be; illustrated by reactions involving a se'condaryalkyi amine, or a secondary aralkyl amine, or a secondary alicyclic amine, such as dibutylamine, dibenzylamine, dicyclohexylamine, or mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylating agent, such as dimethyl sulfate. In a somewhat similar procedure the secondary amine of the kind just specified can be reacted with an alkylene oxide such as ethylene oxide, propylene oxide, or the like, and then reacted with an imine followed by the iinal stepnoted above in order. to convert the primary amino group into a secondary amino group.

Reactions involving the same two classes of reactants previously described, i. e., a secondary amine plus an imine plus an alkylating agent, or a secondary amine plus an alkylene oxide plus an imine plus an alltylating agent, can-be'applied to another class of primary amines which are particularly desirable for the reason that they introduce a definite hydrophile effect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether mines of the formula:

Nam-111.0.)

The-latter patent des'crib'e's typical lialoalk'y'letlierssuc'has Such 'haloalkyl ethers can react with ammonia, or with a primaryamine such as methylamine, 'ethylamine, cyclohexyla'mine,-etc., to produce a sec'on'dary amine of the kind above described, in which o'nefof the groups attached to nitrogen is typified by R, Such hal'oalkyl others also can be'reacted with 'alt'r'iindiiiato give secondary amines as described in the first of th'e 'two patents mentioned immediately preceding. Monoamines 'so'o'btained and suitable for conversioninto appropriate polyamines are exemplified by (CHsOCHzCHzCHaCHaCHzCHa'hNH Other somewhat similar secondary monoainines equally suitable for such conversion reactions in orderto yield tion RO (CH1):

as described in U. s. Patent No. 2,375,659, aired Ma 8, 1945, to Jones at al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl,-etc.

Other suitable s'econdary-'amines which can beconverted into appropriate polyamines can be obtained from products which are sold 'in 'the 'opeh market, such as may be obtained by alkyiation of cyclohexylmethylamine or the alkylation of similar primary oi; for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September'ZO, 1949, to Ka'sztlb'a, provided there is 'no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma-plienoityiiro'p'ylamine, beta-phenoxy-alpha-methylethylaniine, 'and betaphenoxypropylamine.

Other secondary monoamines suitable for v'co'riv er'sion into polyamines are the kind described in British Patent No. 456,517 and may be illustrated by In light of the various examples of polyamines which have been used for illustration it may be well to refer ngain to the fact that previously the amine was shown as appropriate secondary amines, are those of the composi- 6 In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different than if the reaction took place at the intermediate secondary amin'o radical as difierentiated from the terminal group. Again, referring to the second formula above, although a terminal amino radical is not involved it is obvious again that one could obtain two different structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending whether the reaction took place at "either one of the two outer secondary amino groups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde as illustrated by the above examples it is obvious that 5 one might get a mixture in which in part the reaction CH: CH:

NcsHsNc nrNcsniNcsatN H V H H Over and above the specific examples which have appeared previously, attention is directed to the fact that added suitable polyamines are shown in subsequent Table IV.

PART 6 The products obtained by the herein describedprocesses represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difiicult to actually depict the finalproduct of tllfie cogeneric mixture except in terms of the process tse Previous reference has been made to-the fact that the procedure herein employed is comparable, in a general way,.to that which corresponds tosomewhat similar derivatives made either from phenols as differentiated-from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in 0 Bruson Patent No. 2,031,557 in order to obtain a heat- 23 Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early. or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one'which canbe'removed readily at a comparatively'moderate temperature, for instance, at 150' C. A suitable solvent is'usually benzene, xylene, or a comparable petroleum hydrocarbon or amixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solventsarenot here included as raw materials. ;'Ihe reaction-can;beconducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. ,However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcoholscan be used or one can use a comparatively non-volatilesolvent such as dioxane or the diethylether of ethylene glycol. ;.,One can also use a mixture of henzene,or;xylen e and such oxygenated solvents. Note that theuse of, ,suchoxygenated solvent is not required in the sensethat itis not necessaryto'use an initial resin which a is soluble only in an oxygenated solvent as justnoted, and;" it ;is;. not'necessary to, have a'single phase system for r eaction..;-;.':.

Actually; water is apt to belpresent as a solvent for the reason that in-most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, Or it may be diluted down to. about 30% formaldehyde. ,LHowe'ver, paraformaldehyde can be usedbut it is moredifiicult perhaps to add a solid mate'- rial instead of the liquid solution, and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end-of the process, no problem is'involved if the materialis used for any subsequent reaction. However, if the reaction mass is going to be subjected to somefurther reaction where the solvent may beobjectionable as in the case of ethyl or hexyl, alcohol, and if there is tobe subsequent oxyalkyla- 'tion,. then, obyiously,'ithe alcohol-should not be used or else itshould be removed: The fact that an oxygenated 'solvent'need not beemployed, of course, is an advantage for reasons stated." j

Another factor, as far as the selection of solvent goes, is whether or not the cogeneric mixture obtained at the "end of the reaction is tobe used as such or in the salt form.*"i'Ilie""eogene ricmixtures obtained'are apt to be solidsforthickyiscous liquids in which there is some I change-from {the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal." Even if onestart's with a resin which is almost 'wa'terwhite in color, the products obtained are. almost invariably a darlcr'ed in color or at least a red-amber, or some "color whichincludesboth an amber component and a 'reddish'compone'nt: i} By and lflise'; thenichins p nti apt to be lower'andthe" products may be morelsticky and more t'scky'f than th'e'forigl'nal mm itself. "1 jDependingfon the resin selected and on the amine selected the condensation product or reaction mass on a ,solvent-free basis may be hard, resinous and comparable to the resin itself.

' The products obtained, depending on the reactants selected, maybe water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble f Water solubility is enhanced, of course, bymaking a solution in the; acidified vehicles such as a dilute solutionrfor instance, is 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed'out that frequently it is. convenient-to eliminate all solvent, using a temperature of not over 150' C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirableor necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, xylene. or the like, depends primarily on cost, i. e., the use of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? (b) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation? and the third factor is this, (c) is an effort to be made to purify the reaction mass by the usual procedure as, for example, a waterwash to remove the water-soluble unreacted formaldehyde, if any, or a water-wash to remove any unreacted water-soluble polyamine, if employed and present after reaction? .Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, we have found xylene the n cstsatisfactory solvent. I I w We have found no' particularadvantage inusing a low temperaturejfinlthe'early stage of the reaction because, and for 'reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure.

There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30' to 40' but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is notacritical, in' fact, it may be anything from at'ew hours up to 24 hours. I have not found any case where it was necessary or even desirable to hold the lowtemperature stage for more than 24 hours. In fact,we are not convincedthcre is any advantage in holding it-at this stage for morethan 3 or '4 hou'rs'at th'e'most. This, again, is a matterof convenience largely ,fOr -one reason. In heatingand stirring the reaction mass there is a tendency for formaldehyde' to be'lost. Thus, ifthe reaction can be conducted at alower, temperature so as to use up part of the formaldehyde'atsuchlower' temperature, thenthe amount of unreacted formaldehyde is decreased subsequently and T makes. it, easier 'to prevent. any loss. Here, again, this lower temperature is not necessary by virtue of heat con- -vertibility as previous referred to. l

If sol v 'e ts,and'rea'ctants are selected so the reactants and products of reaction are i mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This 'mutual solubilityiis not necessary as previously pointed out :but maybe convenient (under certainv circumstances.

On theother hand, if the products are not mutually soluble then agitation should be more vigorous for the reason 7 that reaction probably takes place principally at the interfaces and the ntore'vigorous the agitation'them'ore interfacial area. The general'procedure employed is'invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned for a number of reasons.

U. S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and-stirred. Depending on the polyamine selected, it may or may-notibe'soluble in the resin solution. If it is not soluble .in-the resin solution it may be soluble in the aqueous formaldehyde solution. 4 If so, the resin then will dissolve in the formaldehyde solution as added, and if'not,'-it..is even possible that the initial reaction mass couldfbe azthree-phase'system instead of a two-phase system..-althoughsthis would be extremely unusual. This solution, or mechanical mixture, if-not 'completelysoluble is cooled to at least the reaction'gtemperature' or {somewhat below, for example 35 C. .{or slightly lower, provided-,thisjuitial low temperature stage ,is employed. The formaldehyde is then added in a suitable form.- For -reasonsipointed-out we prefer to-use a solution-and whether to use a commercial 37% concentration is simply a. matter of choice. In large scale manufacturing there may-besome advantage in using a 30% solutionof formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier tocontrol unreacted formaldehyde loss.

On a large scale if there is any difficulty with formaldehyde 'losscontrol, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction canbeconducted in an autoclave and no attempt made to remove water until the reaction is'over. Gen- =erally speaking, such a procedure is much-less satisfactory v For example,'the reactiondoes not-seem to go to coinpletiomfoamingtakes"place, and other mechanical or chemical difiiculties are'involved. We have found no advantage in using solid formaldehyde because eirenhere=water of reaction is'jformed.

Returning again tothe preferred method of reaction andparticularly from the standpoint of laboratory procedure employing a ;glass resin pot, when the reaction "has-proceeded as one can reasonably expect at a'low temperature, '=for instance, after holding the reaction mass 'withor without stirring,depending on ,whetherqor not it is homogeneous, at 30 or 40 C. for 4 or5 hours, 'or at the-most, up to -24 hours, we then 'completethe reactiOn-by -raising; the temperature up tel-50 C., or thereabouts 'as required. The initial A low temperature procedure can be eliminated or reduced to merely ,theshortest period'oftime ,which avoids loss of polyamine orform-aldeliycle. At a higher temperature we use a phase separating .trap' and,subject the -mixture to reflux condensation-until the water of reaction-and'the 'water of solution of the form'aldehyde is 'eliminat ed. We ,then permit the temperature to riseto-somewhere about 100" C., and generally slightly above 100 C.and below'lSO' C. by eliminating the solvent or part of thegsolventsothe reaction mass stays within this predetermined'range. This period of heating and refluxing, after the'wateris eliminated, iscontinueduntil the reaction massisihomogeneous and then for one to three hours-longer. -The'removal of the solvents is conducted in a conventional manner in the sameway as' the removal of solvents 'in' resin manufacture as described in aforementioned-US. Patent No;2,'499 ,'368.

Needless tosay, as far as the ratio of reactants goes we have'invariably employed approximately'one mole'of the resin based on the molecular weight'of the'resin molecule, 2 moles of the secondary polyaminrand 12 molesof formaldehyde. In some instances we have added a trace of caustic as an added catalystbut have found no particular advantage in this. In other cases we haveused a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excessofamine and, again, have not found any particular advantage in-so doing. Whenever feasible we have eheckedthe completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances havechecked whether-or snot-the end'product 30 hours.

ucts. The following example will serve byway or illustration:

Example 1b The phenol-aldehyde resin is the zone thatfhas been identifiedpreviously as Example 2a. It was-obtained from a para-tertiary butylphenol and? formaldehyde. The resin was prepared using an acidcatalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin 'was 882.5. This corresponded to an average of about 3% phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei,-excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color. A

882 grams of the resin identified as 2a preceding were powdered and mixed with a somewhat lesser weight of xylene, i. e., 600 grams. The mixture wasrefiuxed until solution was complete. It was then adjusted to approximately 30' to 35' C. "and 176 grams of symmetrical dirnethylethylene diamine added. The mixture was stirred vigorously and formaldehyde added slowly. In this particular instance the formaldehyde used was a 30% solution and 200 grams wereemployed which were added in a littleshort of .3 hours. The mixture was stirred vigorously and kept within a temperature range of 30- to 46 C. for about 19 hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from'time to time. The presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within approximately two to three hours after refluxing started. As soonas the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all the water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately 152 C., or slightly higher. The mass was kept at this higher temperature for three to four hours and reaction stopped. During this time, any additional water which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in thecogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red' in color and had the consistency of a sticky fluid or tacky resin. The overall time for reaction was somewhat less than In other examples, it varied from a little over 20 hours up to 36 hours. The time can be reduced by cutting the low'temperature period to approximately 3 to 6 hours. 7

Note that in Table IV following there are a large number=ofaddedexamples illustrating the same procedure.

In each the'initial mixture was stirred and held at a fairly-low temperature'(30' to 40' C.) fora period of several-hours. Then refluxing was employed until the odor offormald'ehyde disappeared. After'the odor -of formaldehyde disappeared the phase-separating trap was employed toseparate out allthe water both the solution and condensation. After all the water had been separated enough xylene-was taken out'to have the final product reflux-for several hours-somewhere in the range of to C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the-watenhad been removed.

"Notethat-a's pointed out previously, thi

procedure is illustrated'by 24examplesin Table IV.

TABLE IV Strength oi Rcnc- Resc- Max. Ex. Resin Amt., Amine used and amount lormal- Solvent used tion tion distill No. used grs. dehyde soln. and amt. tend) time tem and amt. (hi-s.)

882 Amine A, 170 1r 3 200 g..- Xylene, 600 g. 20-23 20 152 480 Amine A, 885 80 100 g... X 20-21 24 150 633 .....do.. 20-22 28 151 441 Amine B, 116 5 -28 30 144 480 do-. 22-30 150 633 ...-..do.' Xylene, 600 g. 21-28 32 150 882 Amine O, 204 I 200 g..- 0 2l-23 30 145 480 Amine O, 102 I 37 100 3... Xylene, 450 3... 20-25 148 633 .'....do Xylene, 500 g. 20-27 35 143 87%, 81 5.... Xylene, 425 g..- 20-22 31 145 --..-do Xylene, 500 g.-' 21-26 24 146 do--..1. Xylene, 550 3.- 22-25 36. 151 ..do Xylene, 400 5... 25-38 32 150 ...do -.d0 21-24 30 162 .-...do Xylene, 550 g. 21-26 27 145 80%,100 g... Xy one, 400 g... 20-23 25 141 ....-do.-.- o 22-21 29 143 .do Xylene, 450 g. 23-25 36 149 .....do...... .....do 21-26 32 148 .....do Xylene, 500 3... 21-23 30 148 do do 20-26 36 162 .....do.... .....do.- Xylene, 440 g. 21-24 32 150 595 Amine H, 282 g 8 81 g...- Xylene. 500 g.-- 21-28 25 150 2 270.--- 391 Amine H, 141 3--.- Xylene, 350 g. 21-22 28 151 As to, the formulas of the above amines referred to as 25 stances. In other words, the 2 moles of the amine- AmineA through Amine H, inclusive, see immediately below:

, H H Amine 11- v Ncmm CH; 7 CH1- n H Amine B- NC|H4N CsHl 03H:

' H H Amine 0- -IOaHsN CH: CH:

H Amine n- Nc,mgc,mr I OH: OH:

H: H: /CC Amine E- 0 N CsHIEHtHI o-c Ha Ha /H Amine F CHKOCsHI) (NCHsCHsCHsN CH: CH: Amine G- NcgHiNcsHiNcsHeN H H H Amine H- CHa-CH, CHgCH CHsO-C CNH-CsHaNH-C 0-0011:

CHs-C 01120 I PART 7 The products obtained as herein described by reactions involving amine condensates and diglycidyl ethers'or the equivalent are valuable for use as such. This is-pointed out in detail elsewhere. However, in many instances the derivatives obtained by oxyalkylation are even more valuable and from such standpoint the herein described products may be considered as valuable intermediates. Subsequent oxyalkylation involves the use of ethylene oxide, propylene oxide, butylene oxide, glycide, etc. Such-oxyalkylating agents are monoepoxides as difiercntiated from polyepoxides.

It becomes apparent that if the product obtained is ,to be treated subsequently with a monoepoxide which may require a pressure vessel as inthe case of ethylene oxide,

it is convenient to use the samereaction vessel inbothin-E modified phenol-aldehyde resin condensate would be reacted with a polyepoxide and then subsequently with a monoepoxide. In any event, if desired the polyepoxide reaction can be conducted in an ordinary reaction vessel, such as'the usualglassgl-aboratory equipment. This is particularly true of the kind used for resin manufacture as described in a number of patents, as for example, U. S. Patent No. 2,499,365.

Cognizanoe should be taken of one particular feature in connection with the reaction involving the polycpoxide and that is this; the amine-modified phenol-aldehyde resin condensate is invariably basic and thus one need not add the usual catalysts which are used to promote such reactions. Gcnerallyspeaking, the reaction will proceed at a satisfactory rate under suitable conditions without any catalyst at all.

Employing polyepoxides in combination with a nonbasic reactant the usual catalysts include alkaline materials such as caustic soda, caustic potash, sodium methylate, etc. Other catalyst may be acidic in nature and are of the kind characterized by iron and tin chloride. Furthermore, insoluble catalysts such as clays or specially prepared mineral catalysts have been used. If for any reason the reaction did not proceed rapidly enough with the diglycidyl ether or other analogous reactant, then a small amount of finely divided caustic soda or sodium methylate could be employed as a catalyst. The amount generally employed would be 1% or 2% It goes without saying that the reaction can take place in an inert solvent, i. e., one that is not oxyalkylationsusceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or elsea similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar eth'ers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in parton the subsequent use of the derivatives or reaction products. If the reaction products are to be rendered solvent-free and itis necessary that the solvent be readily removed as, for example, by the use of vacuum distillation, thus xylene or anaromatic petroleum will serve. If the product is going to be subjected to oxyalkylation subsequently, then the solvent should be one which is not oxyalkylationsusceptible. It is easy enough to select a suitable solvent if required in any instance but, everything else being equal, the solvent chosen should be the most economical one.

, Example 10 The product was obtained by reaction between the diepoxide previously designated as diepoxide 3A, and condensate 2b. Condensate 2b was obtained from resin 52:. Resin 5a was obtained from tertiary amylphenol and formaldehyde.- (Zendensate 2b employed as reactants resin 5a and the amine designated as Amine A at the end of Table IV which is symmetrical dimethyl ethylenediamine. The amount of resin employed was 882 grams; the amount of symmetrical dimethyl ethylenediamine employed was 176 grams; and the amount of 30% formaldehyde employed was 200 grams. The amount of solvent was approximately'fiilo'grams. All this has been described previously.

The solution of the condensate in xylene was adjusted to a 50%5'olutioh. In'this particular instance, and in 30 However if the material was dissolved in an oxygenated solvent and then shaken with 5% gluconic acid it showed a definite tendency to disperse, suspend, or form a sol, and

particularly in a xylene-methanol mixed solvent as previously described, with or without the further addition of a little acetone. 7

The procedure employed of course is simple in light of what has been said previously and in eficct is a procedure similar to that employed in the use of glycide or methylglycide as oxyalkylating agents. See, for example,

Part 1 of U. S. Patent No. 2,602,062 dated July 1, 1952, I

to De Groote.

Various examples obtained in substantially the same I manner are enumerated in the following tables:

TABLE V on- Dle Time Max. Ex. den- Amt., 01:1 0 Amt., xylene, Molar oi reactem m, Color and physical state No. late m. 7 used grs. grs. ratio tion,

used hrs.

10..-. 116 8A 17 133 2:1 6 160 Dark semi-solid.

122 8A 17 139 2:1 7 165 Do. 111 8A 17 128 2:1 6 162 Do. 119 3A 17 136 2:1 6 170 D0. 50..-. 1 120 8A 17 137 2:1 6 160 Do.

159 8A 17 176 2:1 8 168 Dark solid mass. 7 122 8A 17 139 2:1 7 165 Do. 80.... 18b 143 3A 17 160 2:1 8 170 D0. 90.-.. 1 140 8A 17 157 2:1 8 162 Do. 146 8A 17 163 2:1 8 165 Do.

TABLE VI 1 Con- Die Time Max. Ex. don- Amt., oxi e Amt., Xylene, Molar oi reactengn, Color and physical state No. sate grs. used grs. grs. ratio tion,

used hrs.

1D.-..-- 116 B1 27.5 148. 2:1 7 162 Dark semi-solid.

122 B1 27. 5 149. 5 2:1 6 165 Do. 111 B1 27. 5 188. 5 2:1 7 160 Do. 119 B1 27. 5 146. 5 2:1 8 165 Do. 5D... 1 120 B1 27. 5 147. 5 2:1 8 168 D0. 6 159 B1 27. 5 186. 5 2:1 8 160 Dark solid mass. 7D.- 122 B1 27. 6 149.5 2:1 7 160 D0. 8D..- 143 B1 27. 5 170. 5 2:1 8 162 Do. 9D.... 1 140 B1 27. 5 167. 5 2:1 8 160 D0. D... 146 B1 27. 5 173. 5 2:1 8 165 Do.

Solubility in regard to all these compounds was substantially similar to that which was described in Example 10.

practically all the others which appear in a subsequent t'ab1e,"the examples are characterized by the fact that no alkaline catalyst was added. The reason is, of course, that the condensate as such is strongly basic. if desired, a small amount of an alkaline catalyst could be added, such as finely 'p'o'wderedcaustic soda, sodium methylate, etc. If such alkaline catalyst is added it'may speed up the reaction but i't-also may cause an undesirable reactibh,"such a's the polymerization of a diepoxide.

In anyev'e'rit, 116'g'rams or the condensate dissolved ina'pproximately'116 'grams 'of xylene were stirred and heatedt'o 1'0'0"-C. 17 mm or the diepoxide previously identifiedas 3A and dissolved in-an equal weight of xylene'were added 'di'op'wise. An initial addition of the xylene solution carri d the't'e'mpe'rature to 109 C. The remainder-ofdiepoxidewas added in approximately one h'ou'r"sftirn'e. Duri'ng'this period'thete'mperatu'rc rose to ab'o't'i '1'1'8"*C. -'In-'predu;t"wss allowed to reflux at a temperature of {about 128"1C. using-a phase-separating 't'i-a'p. assmau uneuurer x'yl'e'rie'was removed by means of 'the phase-sepa'rating' trap so-' the refluxing temperature rese le s-maximum or 160' C. The mixture was then refluxed at160'.-C. for"ab6ut"6 hours until'the reaction 'st'opped and-ftlie'xylene which had-been removed during the reflux period was returned to the mixture. A small amount of material was withdrawn and the xylene evaporated on the hot plate in ofder to examine the physical properties. The material was a dark red viscous semisolid. It was insoluble in water, it was insoluble in 5% gluconic acid, and it was soluble in xylene, and particularly'ina mixture -01 80% xylene-and 20% methanol.

TABLE VII Probable Resin eon- Probable Amt. oi Amt. of number 01 Ex. No. 'dcnsate mol. wt. of product, solvent, liydroxyls used reaction grs. grs. per moleproduct culc 2, 660 2, 665 1, 335 l1 2, 772 2, 780 1, 394 ll 2, 560 2, 564 1, 284 11 2, 716 2, 720 1, 362 11 2, 748 2, 750 1, 376 11 3,516 3, 522 1, 762 ll 2, 784 2, 790 1, 398 l 1 3,196 a. 200 1,602 11 3, 144 3, 150 l, 578 12 3, 252 3, 250 1, 624 12 TABLE VIII Probable Resin con- Probable Amt. oi Amt. oi number 01 Ex. No. densate mol. wt. of product, solvent, hydroxyls used reaction grs. grs. per moleproduct cule At this point it may be desirable to direct attention to two facts, the first being that we are aware that other diepoxides free from an aromatic radical as, for example, epoxides derived from ethylene glycol, glycerine, or the like, such as the following:

H n H E H n n HOCOO--CCOCOH H g H H H H H H Hc--oc-co0-0U H maybe employed to,replace the diepoxides herein described. However, such'derivatives are not included as part of the instant invention.

At times we have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the mollal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, withan inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the diethyl ether of ethyleneglycol may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the-temperature of reaction by adding a small amount of initially lower boiling solvent such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than apparently the theoretical amount'of diepoxide, for instance, 90% to 95% instead of 100%. The reason for. this fact may reside in the possibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule may actually vary from the true moleculariweight .by several percent.

Previously -the condensate has been depicted in a ticularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in 'connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

In practicing the present process, the treating or known to the art, described, for exampleyin Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto 'for a description of conventional prosimplified form which, for convenience, may be shown thus:

(Amine)CHs(Resin)CHs(Amine) Following such simplification the reaction product with 'a polyepoxide and particularly a diepoxide, would be indicated thus:

[(Amlne) cmmesm CH (Amlne)]\D [(Amlne) GHs(Resln) CHs(Amlns)( in which D.G.E. represents a diglycidyl ether as specified. If the amine happened to have more than one reactive hydrogen, as in the case of a hydroxylated amine or polyamine, having a multiplicity of secondary amino groups it is obvious that other side reactions could take place as indicated by the following formulas:

condensate with a polyepoxide and particularly diepoxioe as herein described.

PART 8 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, parcedures of demulsifying, including batch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

The demulsifier of the present invention, for example, the product of Example 1C, 20%;

A cyclohexylamine salt of a polypropylated napthalene monosulfonic acid, 24%;

' An ammonium salt of a polypropylated napthalene monosulfonic "acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by first (A) condensing (a) an oxyalkylationsusceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction in which R is an aliphatic hydrocarbon radical having at amulsifying agent is used in the conventional way, well 33 least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at temperatures sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be beatstable and oxyalylation-susceptible; followed by (B) reacting said resin condensate'with a phenolic polyepoxide free from reactive functional groups other than epoxy and hydroxyl groups and cog'enerically associated compounds formed in the preparation of said polyepoxides; said epoxides being monomers and low molal polymers not exceeding the tetramers; said polyepoxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (bb) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the'ketonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehyde oxygen atom, the divalent radical H H .g c H H the divalent obtained from a phenol of the structure in which R, R", and R'" represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solventsoluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; said reaction between (A) and (B) be conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the phenolic polyepoxide.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by first (A) condensing (a) an oxyalkylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial ab- .34 sence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the-polyaminegbe free, from any primary amino; radical, anysubstituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point ofthe reactants and resultants of reaction; and-with the proviso, that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting phenolic epoxides being principally polyepoxides, including phenolic diepoxides; said epoxides being free from reactive functional groups other than epoxy and hydroxyl groups, and including additionally cogenerically associated compounds formed in the preparation of said polyepoxides and diepoxides; said epoxides being monomers andlow molal polymers not exceeding the tetramer; said epoxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined ,without an intervening radical, and (bb) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ltetonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical S-S, said phenolic portion of the diepoxide being obtained from a phenol of the structurein which R, R", and 11'' represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; with the further proviso that said reactive compounds (A) and (B) bemembers of the classconsisting of nonethermosetting organic solventsoluble liquids and low-melting, solids; with the final proviso that the reaction product, be a member of, the class of solvent-solubleliquidsand low-melting solids; and said reaction between (A) and (B) be conducted below the pyrolytic point 0! the reactants and resultants of reaction. I

3; A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifler, said demulsifier being obtained by first (A) condensing (a) an oxyalkylation-susceptible, fusible, nonoxygenated organic solvent-soluble water-insoluble, low-stage :phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the-process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting a phenolic diepoxide free from reactive functional groups other than epoxy and hydroxyl groups,- and cogenerically associated compounds formcd'in the preparation of said diepoxides; said epoxidcs being monomers and low molal polymers not exceeding the tetramers; said epoxides being selected from the class consisting'of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (bb) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical selected from'the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical the divalent radical, the divalent sulfonc radical, and the divalent monosulfide radical the divalent radical CH:SCH:, and the divalent disulfide radical 4-S-; said phenolic portion of the diepoxide being obtained from a phenol of the structure in which R, R", and R'" represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; with the further proviso that said reactive compound (A) and (B) be members of the class consisting of non-thcrmosetting organic solventsoluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solvcnt'soluble liquids and low-melting solids; and said reaction between (A) and '(B) be conducted below the pyrolytic point of the reactants and the resultants of reaction.

4. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emul sion to the action of a detmflsiller, said-demulsifier being obtained by first (A) condensing (a) lion-susceptible, fusible, nonoxygenated organic solventsoluble water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the fur-.

ther proviso that the polyamine be free from any primary amino radical, any substituted irnidazolinc radical, and any substituted tetrahydropyrimidine radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and rcsultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting a phenolic diepoxide free from reactive functional groups other than epoxy and hydroxyl groups, and cogencrically associated compounds formed in the preparation of said dicpoxides; said epoxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (bb) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone residues formed by the elimination of the kctone residues formed by the elimination of the ke tonic oxygen atom, and aldehyde residues obtained by the elimination of the 'kctonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical I monosulfide radical --S, the divalent radical CHaSCHaand the divalent disuifide radical -SS-; said phenolic portion of the diepoxide being obtained from a phenol of the structure in which R, R", and R represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; the ratio of reactant (A) to reactant (B) being at least sufficient so there is available at least one active hydrogen in (A) for each oxirane ring in the diepoxide reactant (B'); with the further proviso that said reactive compounds (A) and an oxyallcyla- In (B) the members of the class consisting of non-thermoleast 3 and not over 6 phenolic nuclei p'er resin molecule;

said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive'toward said phenol; 'said resin being formed in the substantial absence'of triflinctional phenols; said phenol being oftheformula" OH in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and formaldehyde; said condensation reaction being conducted at a temperature sufllciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; andwith the-proviso that the resinous condensation product. resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting a phenolic diepoxide free from reactive functional groups other than epoxy and hydroxyl groups, and cogenerically associated compounds formed in the preparation of said diepoxidee, including monoepoxides; said cogenerically associated compounds containing an average of more than one epoxide group per molecule; said cpoxides being monomers and low moial polymers not exceeding the tetramers; said epoxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (bb) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical selected from' the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical o o-o{ Ks H H:

the divalent radical, the divalent sulfone radical, and the divalent monosulfide radical S, the divalent radical portion of the diepoxide being obtained from a phenol of the structure in which R', R", and R'" represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; the ratio of reactant (A) to reactant (B) being at least sufiicient so there is available at least one active hydrogen in (A) for each oxirane ring in the diepoxide reactant (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

6. A process for breaking petroleum emulsions of the water-in-oil'type characterized by subjecting the emulsion to the action'of a demulsifier, said demulsifier being obtained by first (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aide-s hyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula lated polyamine having at least onesecondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water-and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-suseeptible; followed by (B) reacting a member'of the class consisting of (aa) compounds of the following formula in which R represents a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonie oxygen atom and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical '39 the divalent radical, the divalent sulfone radical, and the divalent monosulfide radical S, the divalent radical CHaSCHaand the divalent disulfide radical 44-; and R is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol in which .R'. R", and 11'" represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; the ratio of reactant (A) to reactant (B) being at leastsufiicient so there is available-at least oneactive hydrogen in (A) for each oxirane ring in the diepoxide reactant (B); n represents an integer selected from the class of zero and 1, and n reprecents a whole. number not greater than 3; and (bb) cogenerically associated compounds formed in the preparation of (aa) preeeding,.including monoepoxides; with the further proviso that said reactive compounds (A) and .(B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and'low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactanm and the resultants of reaction.

7. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by first (A) condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aidehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunetional phenols; said phenol being of the formula in which R"" is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and subtituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalltylation-susceptible; followed by (B) reacting a member of the class consisting of (.aa) compounds of the following formula:

wherein R is an aliphatic hydrocarbon "tidge, each n independently has one of the values 0 to l, and R1 is an alkyl radical containing from 1 to 12 carbon atoms, and (bb) cogenerically associated compounds formed in the preparation of (an) preceding, including monoepoxidcs; with the proviso that (B) consist principally of the monomer as distinguished from other eogeners; the ratio of reactant .(A) to reactant .(B) being at least sufficient so there is available at least one active hydrogen in (A) for each oxirane ring in the diepoxide reactant (B); with the further proviso that said reactive compounds (A) and (B) be members of the classconsisting of nonthermosetting organic solvent-soluble liquids and lowmelting solids; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

8. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the-action of a demulsifier, said demulsifier being obtained by first (A) condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at ie-ast 3 and not over 6 phenolic nuclei per resin molecule; .said resin being difunctional only in regard to methyiol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula and (c) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting a member of the class consisting of (aa) compounds of the following formula and (bb) cogenerically associated compounds formed in the preparation of (aa) preceding, including monoepoxides; with the proviso that (B) consist principally of the monomer as distinguished from other eogeners; the ratio .of reactant (A) to reactant (B) being at least sufflcient so-there is available .at least one active hydrogen in (A) for each oxirane ring in the diepoxide reactant (B); with the further proviso that said reactive compounds (A) a e mem ers of the class consist- 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER, SAID DEMULSIFIER BEING OBTAINED BY FIRST (A) CONDENSING (A) AN OXYALKYLATIONSUSCEPTIBLE, FUSIBLE, NONOXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOLFORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 